Process for preparing polymers from ethylenically unsaturated glycidyl monomers

ABSTRACT

In the process for the preparation of finely divided high polymers of a cross-linked structure comprising polymerizing a monoethylenically unsaturated monomer and a diethylenically unsaturated monomer, in an organic solvent, an improvement characterized in that prior to the polymerization a linear polymer selected from the group consisting of hot n-heptanesoluble monoolefin polymers, polyalkylene oxides and vinyl chloride polymers is dissolved in said organic solvent.

United States atent Mizutani et al. 5] 23, 1972 [54] PROCESS FORPREPARING POLYMERS FROM ETHYLENICALLY [56] References Cited UNSATURATEDGLYCIDYL M 0 NOMERS UNITED STATES PATENTS 3,423,481 l/l969 Mitzutani etal ..260/836 [72] Inventors: Yukio Mizutani; Seishiro Matsuoka, both ofTokuyama-shi, Japan [73] Assignee: Tokuyama Soda Kaubushiki Kaisha,

Tokuyama-shi, Japan [22] Filed: Nov. 25, 1969 [21] Appl.No.: 879,697

[51] Int. Cl C08g 45/04, C08g 39/10, C08f 37/1 8 [58] Field of Search..260/836 3,301,919 l/l967 Cenci ..260/836 Primary ExaminerPaulLieberman AztorneySherman and Shalloway [57] ABSTRACT In the process forthe preparation of finely divided high polymers of a cross-linkedstructure comprising polymerizing a monoethylenically unsaturatedmonomer and a diethylenically unsaturated monomer, in an organicsolvent, an improvement characterized in that prior to thepolymerization a linear polymer selected from the group consisting ofhot nheptane-soluble monoolefin polymers, polyalkylene oxides and vinylchloride polymers is dissolved in said organic solvent.

6 Claims, No Drawings PROCESS FOR PREPARING POLYMERS FROM ETHYLENICALLYUNSATURATED GLYCIDYL MONOMERS This invention relates to a process forthe preparation of finely divided high polymers having excellentdispersibility in organic solvents and resins. More particularly, itrelates to an improved process for the preparation of finely dividedhigh polymers of a cross-linked structure containing a functional groupexhibiting by itself an affinity for dyestuffs.

It is generally known to improve the dyeability of difficulty dyeablepolymers such as polyethylene, polypropylene, polyesters, e.g.,polyethylene terephthalate, and polyvinyl chloride by blending therewitha polymer having an affinity for dyestufs. For instance, thespecifications of U. S. Pat. No. 3,423,481 and British Pat. No.1,132,645 teach the blending of a difficulty dyeable polymer with afinely divided high polymer ofa particle size of less than 1 micronhaving a crosslinked structure and being obtained by polymerizing amonoethylenically unsaturated monomer containing a functional group,such as glycidyl, methacrylate, with a diethylenically unsaturatedmonomer such as divinyl benzene in the presence of an organic solventwhich dissolves these monomers but not the cross-linked polymer producedand not the corresponding linear polymer containing no diethylenicallyunsaturated monomer; and disclose that in order to disperse the finelydivided high polymer uniformly in the difficultly dyeable polymer it ispreferable to polymerize said monoethylenically unsaturated monomer anddiethylenically unsaturated monomer in the presence of an organicsolvent in which powder of said difficultly dyeable polymer isdispersed.

The finely divided high polymer taught by such prior art has across-linked structure; therefore, it is advantageous in that is isthermally stable and the functionality of the polymer is neither lostnor degraded even if it is blended with the difficultly dyeable polymerunder heating or subjected to melt shaping conditions. However, althoughsuch finely divided high polymer takes a form of fine particles of adiameter of less than 1 micron, it has a property of being easilyagglomerated and hence, it is not always easy to disperse it finely anduniformly in the difficultly dyeable polymer. Of course, the finelydivided high polymer can be relatively uniformly dispersed in thedifficultly dyeable polymer when it is obtained by polymerizing saidmonoethylenically unsaturated monomer and diethylenically unsaturatedmonomer in the presence of the difficultly dyeable polymer of a powderform. But this polymerization method is apparently under variousrestrictions when it is conducted in an industrial large scale.

We have now found that finely divided high polymers of a cross-linkedstructure having a highly improved dispersibility in organic solventsand resins can be obtained when a monoethylenically unsaturated monomerand a diethylenically unsaturated monomer are polymerized in thepresence of a specific polymer dissolved in an organic solvent, moreparticularly, in the presence of a solution of a polymer selected fromthe group consisting of hot heptane-soluble monoolefin polymers,polyalkylene oxides and vinyl chloride polymers in a specific organicsolvent.

Accordingly, it is an object of this invention to provide an improvedprocess for the preparation of finely divided high polymers of across-linked structure comprising polymerizing l a monomeric memberselected from the group consisting of i. at least oneradical-polymerizable monoethylenically unsaturated monomer (a) having afunctional group selected from the group consisting of epoxy, acidanhydride, carboxyl, carboalkoxyl, carbamoyl, acyloxy andnitrogen-containing heterocyclic groups, and

ii. a monomer combination of said monoethylenically unsaturated monomer(a) with a monoethylenically unsaturated comonomer (b) selected from thegroup consisting of monovinyl aromatic compounds, acrylonitrile, vinylchloride and nbutene,

and (2) 0.5 to 30 percent weight, based on the said monomeric member(1), of a diethylenically unsaturated monomer, in an organic solventwhich dissolves said monomers l) and (2) but not the cross-linkedpolymer produced and not the corresponding linear polymer free of saiddiethylenically unsaturated monomer (2) in the presence of afree-radical initiator; characterized in that prior to thepolymerization a linear polymer selected from the group consisting ofhot n-heptanesoluble monoolefin polymers, polyalkylene oxides and vinylchloride polymers is dissolved in said organic solvent in an amount of10 to 500 percent by weight based on the total of the monomers l and(2).

As the monoethylenically unsaturated monomer (a) to be used in thisinvention there max be cited (i) monoethylenically unsaturated monomershaving an epoxy group such as glycidyl esters of ethylenicallyunsaturated carboxylic acids, e.g., glycidyl acrylate and glycidylmethacrylate, glycidyl ethers of ethylenically unsaturated alcoholse.g., allyl glycidyl ether, and 1,3-butadiene monoxide; (ii)intermolecular anhydrides of ethylenically unsaturated dicarboxylicacids such as maleic anhydride and itaconic anhydride; (iii)monoethylenically unsaturated monomers containing a carboxylic groupsuch as acrylic acid, methacrylic acid, maleic acid, fumaric acid,itaconic acid and vinyl benzoic acid; (iv) monoethylenically unsaturatedmonomers containing a carboalkoxyl group such as methyl, ethyl, propyland lauryl esters of acrylic and methacrylic acids; (v)monoethylenically unsaturated monomers containing a carbamoyl group suchas acryl amide and methacryl amide; (vi) monoethylenically unsaturatedmonomers containing an acyloxy group, preferably, derived from a lowerfatty acid, such as vinyl acetate and vinyl propionate; and (vii)monoethylenically unsaturated monomer containing a nitrogen-containingheterocyclic group such as vinyl pyridine, vinyl imidazole, vinylpyrrolidone and vinyl carbazole.

These monoethylenically unsaturated monomers may be used singly or incombination of two or more. Further they may be used in combination withother monoethylenically unsaturated comonomer (b), which includesmonovinyl aromatic compounds such as styrene, vinyl toluene, a -methylstyrene and vinyl ethyl benzene; acrylonitrile; vinyl chloride andn-butene. In case the monoethylenically unsaturated comonomer (b) isused, it is generally preferable that the ratio of the monoethylenicallyunsaturated monomer (a) the monoethylenically unsaturated comonomer (b)is within a range from 1 :0.1 to l 10.

As the diethylenically unsaturated monomer (2) to be used in the processof this invention there may be named, for instance, divinyl benzene,divinyl toluene, divinyl sulfone and diallyl phthalate. Among thesediethylenically unsaturated monomers, aromatic hydrocarbons having twovinyl groups such as divinyl benzene and divinyl toluene areparticularly preferred for attaining the object of this invention. Theuse of conjugated diolefins of a chain structure such as l ,3-butadieneand 1,3-hexadiene is not suitable for attaining the object of thisinvention, because the introduction of a cross-linked structure into theresulting polymer is difficult when they are used.

The above mentioned diethylenically unsaturated monomer is used in anamount of 0.5 to 30 percent by weight based on the monoethylenicallyunsaturated monomer (1), especially 5 to 15 percent by weight. By usingthe diethylenically unsaturated monomer in an amount within this range,it is made possible to introduce a cross-linked structure into theresulting polymer and obtain a high polymer of a cross-linked structurein the form of fine particles having a diameter of less than 1 micron.

The most characteristic feature of this invention resides in that inconducting the polymerization of the above mentioned mono-ethylenicallyunsaturated monomer and diethylenically unsaturated monomer, a specificlinear polymer is dissolved beforehand into a specific solvent to beused for the polymerization. The linear polymer to be made present inthe polymerization system in the form of a solution in a specificsolvent in the process of this invention includes 1 Polymers ofmonooletins, for instance, expressed by the formula in which R standsfor hydrogen, alkyl of up to four carbon atoms or phenyl and R standsfor hydrogen or alkyl of up to 4 carbon atoms; which are soluble in hotn-heptane, namely, which are dissolved when extracted with n-heptane at98 C. (boiling point of n-heptane); such as atactic polypropylene, lowmolecular weight polyethylene having an average molecular weight of lessthan 30,000, preferably less than 10,000, polyisobutene, atacticpolybutene-l, hot heptane-soluble ethylene-propylene copolymersinclusive of random copolymers and block copolymers, polystyrene, andethylenevinyl acetate copolymers having a vinyl acetate content of to 80percent by weight;

2. Polyalkylene oxides, preferably polymers of an alkylene oxide ofthree to four carbon atoms, such as polypropylene oxide, polybutyleneoxide, propylene oxide/ethylene oxide random or block copolymers, andpropylene oxide/allyl glycidyl ether copolymers; and

3. Polymers of vinyl chloride.

Such linear polymer is made present in the polymerization system in theform of a solution in an organic solvent in an amount of generally 10 to500 percent by weight, preferably 10 to 100 percent by weight, based ofthe total amount of said monoethylenically unsaturated monomer (l) anddiethylenically unsaturated monomer (2).

The organic solvent to be used in the process of this invention shouldmeet the following requirements:

A. It dissolves the above mentioned linear polymer; and

B. it dissolves the foregoing monoethylenically unsaturated monomer (l)and diethylenically unsaturated monomer (2) but does not dissolve thecross-linked polymer produced and not the corresponding linear polymerfree of the diethylenically unsaturated monomer (2), i.e. the linearpolymer consisting only of the monoethylenically unsaturated monomer 1)used.

The class of the organic solvent to be used varies depending on theclass of the linear polymer to be made present in the polymerizationsystem and the classes of the monomers to be used, but an optionalsolvent selected from saturated aliphatic hydrocarbons such as hexane,liquid propane, liquid butane, heptane, cyclohexane, and hydrocarbonmixtures, e.g., petroleum benzine. petroleum ether, ligroine andkerosene; aromatic hydrocarbons such as benzene, xylene and toluene;linear or cyclic aliphatic ethers of up to eight carbon atoms such asdiethyl ether tetrahydrofuran and dioxane; and aliphatic alcohols suchas propanol and n-butanol may be used. It is also possible to use amixture of two or more of such solvents. Of course, these organicsolvents should be substantially inactive to the monomers to be used.

For instance, in case the linear polymer to be made present in thesolution form is a vinyl chloride polymer, tetrahydrofuran is used asthe solvent and in case the linear polymer is a hot heptane-solublepolyolefin, an aliphatic hydrocarbon such as n-heptane and kerosene oran aromatic hydrocarbon such as benzene is used. Further, in case thelinear polymer is a polyalkylene oxide, any of the above cited solventsmay be used optionally.

The foregoing monoethylenically unsaturated monomer l may be classifiedaccording to the class of the organic solvent to be used as a matter ofconvenience as follows:

i, To aliphatic hydrocarbons; acrylic acid, methacrylic acid,styrene-maleic anhydride, methacrylic acid ester-maleic anhydride,acrylic acid ester-acrylonitrile-glycidyl methacrylate, glycidylmethacrylate-vinyl chlorideacrylonitrile, maleic anhydride-vinyltolueneacrylonitrile, Z-methyl-S-vinyl pyridine-methacrylic acid ester,styrene-glycidyl methacrylate, vinyl acetateglycidyl acrylate, glycidylacrylate-styrene, etc.

II. To aliphatic alcohols (for instance, butanol); acryl amide, acrylicacid, methacrylic acid, acryl amidemethacrylic acid, acrylamide-acrylonitrile, vinyl acetatemethacrylic acid, vinylacetate-acrylic acid, vinyl acetateacryl amide, etc.

III. To aromatic hydrocarbons; maleic anhydride, styrenemaleicanhydride, vinyl acetate-maleic anhydride, methacrylic acid, acrylicacid, maleic anhydrideacrylonitrile-styrene, acrylic acid-acrylonitrile,methacrylic acid-acrylonitrile, etc.

IV. To ethers (for instance, dioxane); acrylic acidacrylonitrile,methacrylic acid-acrylonitrile, acrylic acid ester-acrylonitrile,acrylic acid ester-styrene, acrylic acid ester-vinyl chloride, acrylicacid ester-acrylonitrilestyrene, etc.

Those skilled in the art will easily select an optimum solvent to acombination of the linear polymer and monomers to be used by a simpleexperiment in accordance with the foregoing exemplification. The amountof the organic solvent to be used is not particularly critical if it isgreater than 300 percent by weight based on the total amount of themonomers, but from the economical viewpoint it is preferable to use theorganic solvent in an amount of 500 to 1,000 percent by weight based onthe total amount of the monomers.

In accordance with the process of this invention, the above mentionedmonoethylenically unsaturated monomer (l) and diethylenicallyunsaturated monomer (2) are polymerized in a specific organic solventcontaining, dissolved therein, the above mentioned linear polymer. Asthe polymerization initiator there is used a free-radical initiatorsoluble in the organic solvent to be used. As such free-radicalinitiator there may be cited organic peroxides such as benzoyl peroxide,dicumyl peroxide, di-tert.-butyl peroxide and cumene peroxide, and azocompounds such as azobisisobutyronitrile. The initiator is used in acatalytic amount, for instance, 0.1 to 10 percent by weight based on thetotal amount of the monomers. The polymerization may be conducted in acustomary manner in the deaerated system or by removing oxygen from thesystem by blowing in nitrogen. Temperatures adopted in the conventionalradical polymerization methods are also adopted in the process of thisinvention, but it is preferred to carry out the polymerization attemperatures ranging from 50 C. to the boiling point of the solvent. Ofcourse, in this invention the polymerization may be initiated byirradiation of ultraviolet rays or ionizing radical rays in accordancewith conventional techniques instead of using the above mentioned azocompound or organic peroxide.

Thus, in accordance with this invention there can be obtained finelydivided high polymers of a cross-linked structure having a particlediameter of less than 1 micron and containing a functional groupselected from epoxy, acid anhydride, carboxyl, carboalkoxy, carbamoyl,acyloxy and nitrogen-containing heterocyclic groups. The finely dividedhigh polymers obtained in accordance with the process of this inventionhave a remarkedly excellent dispersibility in organic solvents andresins, because they are prepared in the presence of a specific linearpolymer uniformly dissolved in an organic solvent. In fact, inaccordance with this invention, finely divided high polymers formed bythe polymerization are obtained in the form of a stable suspensions inwhich the polymers are uniformly dispersed in organic solvents used, andthe finely divided high polymers exhibit hardly any tendency ofagglomeration or sedimentation. Further, even when one drop of thesuspension of the finely divided high polymer prepared in accordancewith the process of this invention is added, for instance, to 50 c.c. ofan organic solvent and allowed to stand still, a good stable dispersionstate can be maintained.

Further, while finely divided high polymers obtained in accordance withthe above described known method by copolymerizing a monoethylenicallyunsaturated monomer with a diethylenically unsaturated monomer in anorganic solvent free of the above mentioned specific linear polymerdissolved therein exhibit a structural property of forming bunches ofparticles, the finely divided high polymers prepared in accordance withthis invention hardly exhibit such structural property.

Effects of this invention will be clearly seen from the appendeddrawings.

Suspensions of finely divided high polymers in organic solvents preparedin accordance with the process of this invention may be incorporated, asthey are or after a part or all of the organic solvent has been removedby distillation, into various resins, for instance, polyolefins such aspolypropylene, polyethylene, ethylene-propylene copolymers andethylenepropylene-non-conjugated diene copolymers; vinyl chloride resinssuch as polyvinyl chloride and vinyl chloride-vinylidene chloridecopolymers; acrylonitrile; and, polyesters such as polyethyleneterephthalate. Thus, they can improve dyeability of these resins andimpart a delustering effect to them. These effects may be attainedsufficiently by incorporating into such resin 0.1 to percent by weightof the finely divided high polymer of this invention.

Further, it is also possible to introduce into the finely divided highpolymer of this invention dyestuffs, antioxidants, ultravioletabsorbents, and other polymer modifiers or additives by utilizing thefunctionality of the finely divided high polymer, and to blend suchproducts into resins.

Still further, products obtained by introducing dyestuffs into thefinely divided high polymer may be used in forms of suspensions in anorganic solvent as olephilic inks excellent in stability to storing.

This invention will be described more detailedly with reference toexamples.

Example 1 A three-neck distillation flask was charged with g of anatactic ethylene-propylene copolymer having a molecular weight of about7,000 and containing 3.7 percent by weight of ethylene units and 285 ccof n-heptane, and the atmosphere inside the flask was replaced bynitrogen. Then, the flask was placed into a thermostat maintained at 70C., and the temperature inside the flask was raised while stirring to 70C. to dissolve the atactic copolymer into n-heptane. A mixed solution ofa vinyl monomer(s) indicated in Table 1 below in an amount alsoindicated in the table, 3 g of divinyl benzene and 1.2 g of benzoylperoxide was charged into the flask and the polymerization was conductedfor 5 hours. In each run, several minutes after the initiation of thepolymerization the reaction liquor became opaque, and after completionof the polymerization there was obtained a highly viscous white slurrycontaining a finely divided, cross-linked high polymer. A small amountof each product was withdrawn to a sedimentation-test tube and dilutedwith n-heptane to conduct the sedimentation test. With respect to eachproduct, the opaqueness did not disappear even after 24 hours in thesedimentation test.

The sample of Run No l which had been subjected to the sedimentationtest was dropped on a collodion membrane and a photograph thereof wastaken under an electron microscope at a magnification of 6,000. It isseen from this photograph that smallest particles possessed a particlediameter of less than 0.1 micron and that the product had an excellentdispersibility.

The slurry obtained by the polymerization in Run No. l was allowed toflow in a porcelain vat) and the solvent was removed by evaporation toobtain a solid mixture of the resulting finely divided high polymer andthe atactic ethylenepropylene copolymer. The mixture was blended in anisotactic polypropylene in an amount such that the finely divided highpolymer content would be about 3 percent, and the blend was molded intoa pellet by means of an extruder. Then, the pellet was shaped into afilm having a thickness of 0.35 mm. Thereafter, the film was dyed in abath of Miketon Fast Orange (Color Index Number of l 1005) (dispersedye) and a thin slice of the dyed film was photographed under amicroscope at a magnification of l40.From this photograph it is seenthat the finely divided high polymer is dispersed extremely uniformly inthe resin.

Comparative Example 1 Run No. l of Example 1 was repeated without theuse of polymer. The yield of the finely divided high polymer was 88percent. The product was subjected to the sedimentation test. In about 5seconds, the finely divided high polymer was precipitated. Theprecipitated system was agitated again to make the high polymerparticles floating in the system again, and dropped on a collodionmembrane.

Example 2 13.5 G of maleic anhydride, 13.5 g of styrene, 3 g of divinylbenzene and 35 g of an atactic polypropylene having a molecular weightof about 20,000 were dissolved into 300 cc of benzene, and the solutionwas polymerized for 5 hours at 70 75 C. with the use of 1.2 g of benzoylperoxide as an initiator in the open air. Several minutes after theinitiation of the polymerization the system became opaque, and one hourafter the initiation of the polymerization the system bean to take aform of a highly viscous slurry. The yield was 86 percent. The resultingslurry was placed into a porcelain vat to remove the solvent therefrom.A small amount of remaining solid was dry blended in a mixer intopowders of isotactic polypropylene, polyvinyl chloride, polystyrene andpolymethyl methacrylate, separately. Each blend was molded into a pelletby means of an extruder and shaped into a film of a 0.35 mm thickness.Each film was dyed in the same manner as in Example 1 and extracted withacetone. As a result of the observation under a microscope it wasconfirmed that in each sample the finely divided high polymer wasextremely uniformly dispersed in the resin.

Comparative Example 2 The polymerization was conducted in the samemanner as in Example 2 in the absence of the atactic polypropylene. Theyield of the finely divided high polymer was 91 percent. A small amountof the high polymer was dry blended in a mixer into powder of isotacticpolypropylene, and the blend was molded into a pellet by means of anextruder and shaped into a film in the same manner as in Example 2. As aresult of the observation of the film under a microscope, the existenceof agglomerated particles was confirmed. During the dry blending stepthe finely divided, cross-linked high polymer was electrostaticallyfixed to the wall of the mixer.

Example 3 10 G of 2-methyl5-vinyl pyridine, 17 g of acrylonitrile, 3 gof divinyl benzene and 30 g of a low molecular weight polyethylenehaving an average molecular weight of 5,400 were added into 300 cc ofbenzene. After the atmosphere had been replaced by nitrogen, the systemwas placed into a thermostat maintained at 70 72 C. and let to stand inthis state for a period of time sufficient to dissolve the low molecularweight polyethylene. Then, 2.2 g of benzoyl peroxide was added to thesystem and the polymerization was conducted for 5 hours. As a resultthere was obtained a yellowish slurry in which a finely divided highpolymer was dispersed uniformly. The monomer conversion was 48 percent.When the system was allowed to cool to room temperature, theprecipitation of the low molecular weight polyethylene was observed. Asmall amount of the dispersion was thrown into a great excess ofbenzene, and the resulting mixed suspension was dropped on a carbonvacuum evaporation membrane and observed under an electron microscope ofa magnification of 10,000 From the photograph it is seen that particlesof the finely divided, cross-linked high polymer were embraced with thepolyethylene and dispersed therein in a rice grain-like form.

The above slurry containing the finely divided high polymer was throwninto a great excess of methanol and filtrated, followed by washing withmethanol and drying. The resulting solid was blended into a high densitypolyethylene in an amount such that the content of the finely dividedhigh polymer would be about 3 percent. The blend was molded into apellet by means of an extruder and treated in the same manner as inExample 1. As a result of the observation under a microscope it wasconfirmed that the finely divided, crosslinked high polymer wasdispersed uniformly in the polyethylene and that the polyethyleneembracing the finely divided high polymer in such a good dispersioncondition as shown in F IG. 2 was precipitated while it was cooling:Example 4 7.5 G of maleic anhydride, 5 g of styrene, 2.5 g of divinylbenzene and 7 g of polypropylene oxide having an intrinsic viscosity of3.2 dl/g measured in benzene at 35 C. were dissolved in 140 ml ofbenzene at 79 C. under a nitrogen atmosphere while stirring, followed byaddition of 1.0 g of benzoyl peroxide dissolved in 10 ml of benzene. Thepolymerization was conducted at 79 C. for 6 hours. As a result there wasobtained a white slurry containing a finely divided high polymer andbeing rich in flowability at a monomer conversion of 92 percent. A smallamount of the slurry was taken into a sedimentation test tube anddiluted with benzene. Even after the diluted liquor had been allowed tostand for a weak, no sedimentation was observed. The diluted liquor wasfurther diluted and dropped on a carbon vacuum evaporation membrane.Thus, a photograph was taken under an electron microscope. From thephotograph it is seen that a greater particles had a particle size ofabout 0.3 micron and smaller particles have a size of less than 0.03micron, said size being so small that electron rays would almost passtherethrough. Comparative Example 3 The polymerization was conductedunder the same conditions as in Example 4 in the absence of thepolypropylene oxide. As a result there was obtained a polymerizationproduct of a slurry containing a bulky, finely divided high polymer at ayield of 95 percent. At the sedimentation experiment, the high polymerwas completely sedimented within 24 hours. A small amount of the slurryused for the sedimentation test was diluted with benzene and subjectedto an irradiation of supersonic waves of 400 KC and 50 W at 25 50 C. for2 minutes and 30 seconds. Then, the so treated diluted liquor wasdropped on a collidion membrane having a carbon vacuum evaporationmembrane thereon, and a photograph was taken under an electronmicroscope. From this photograph it is seen that the high polymersynthesized in the absence of the propylene oxide is present in the formof agglomerated particles having a much greater size than that of thefinely divided high polymer prepared in Example 4. Example 5 17 Gglycidyl methacrylate, 9 g of acrylonitrile, 4 g of divinyl benzene andl5 g of polypropylene oxide ((1 3.2) were added into 300 cc ofn-heptane, and the mixture was placed in a thermostat maintained at 7072 C. and stirred under a nitrogen atmosphere to dissolve the abovecomponents into the solvent. Then, 1.2 g of benzoyl peroxide was addedto the solution and the polymerization was conducted for 5 hours. Themonomer conversion was 73 percent. After completion of thepolymerization, the reaction product was taken into a porcelain vat anddried in the air at room temperature, followed by drying in vacuo. Asmall amount of the dried product was mixed and kneaded withpolypropylene oxide (the finely divided high polymer content being about3 percent) by means of a roller. Then, the resulting massy product wasdyed under the same conditions as in Example 1, and the excessivedyestufi' not reacted with the glycidyl group was removed by extractionwith methanol. After conducting the drying, the dyed product was fixedon a thin plate of polypropylene, cooled by dry ice and methanolmaintained at -50 C. and cut into thin slices by means of a microtome.As a result of the observation of such slice under a microscope it wasconfirmed that the finely divided high polymer was dispersed quiteuniformly. Example 6 13 G of methyl methacrylate, 14 g of acrylonitrile,3 g of divinyl benzene and 15 g of polyvinyl chloride powder (having amolecular weight of about 10,000 were added into 300 cc of dioxane, andthe mixture was stirred at 70 72 C. under a nitrogen atmosphere. Afterthe polyvinyl chloride powder had been dissolved 1.2 g of benzoylperoxide was added to the system and the polymerization was conductedfor 5 hours. After completion of the polymerization there was obtained aslightly greyish white slurry at a yield of 32 percent. To the slurrywas added 50 g of dioctyl terephthalate as a plasticizer and then theslurry was placed into a vat where the solvent was removed bydistillation to obtain a sheet-like polyvinyl chloride compositioncontaining a finely divided, cross-liked high polymer. The saidsheet-like polyvinyl chloride composition was blended with anotherpolyvinyl chloride in an amount such that the content of the finelydivided high polymer would be about 3 percent, and the blend was kneadedat C. by means ofa mixing roll. Then, the blend was recovered in theform of a sheet and dyed in the same manner as in Example I. As a resultof the observation under a microscope it was confirmed that the finelydivided high polymer was dispersed quite uniformly. Comparative Example4 Example 6 was repeated by employing as solvent n-heptane instead ofdioxane. As polyvinyl chloride was not dissolved in the solvent butsuspended therein. After completion of the polymerization, there wasobtained a homogeneous mixture of the polyvinyl chloride and a finelydivided, cross-linked high polymer. A part of the resulting mixture wasdissolved into dioxane and the sedimentation test thereof was conductedin the same manner as in Example 1. Only several minutes the finelydivided high polymer was sedimented. When the slurry obtained in Example6 was similarly subjected to the sedimen tation test, any sedimentationwas hardly observed even after 24hours. Example 7 12 G of 4-vinylpyridine, 15 g of methylacrylate, 3 g of divinyl benzene and 30 g of anatactic polypropylene having a molecular weight of about 20,000 wereadded into 300 cc of cyclohexane, and the atactic polypropylene wasdissolved under a nitrogen atmosphere by maintaining the temperature at70 72 C., followed by addition of 1.2 g of benzoyl peroxide. Thepolymerization was conducted for 3.5 hours. As a result there wasobtained a slightly yellowish white slurry in which a finely dividedhigh polymer was dispersed quite uniformly. The yield was 47 percent.The slurry was placed in a porcelain vat and the solvent was removed bydistillation. The remaining solid was dry blended in a mixer into powderof an isotactic polypropylene in an amount such that the content of thefinely divided high polymer would be about 3 percent. The blend wasmolded to a pellet by means of an extruder and shaped into a film havinga thickness of 0.35 mm. As a result of the observation of a photographof the section of the dyed film taken in the same manner as in Example1, it was confirmed that the finely divided high polymer was presentexhibiting an excellent dispersibility.

Example 8 27 G of glycidyl methacrylate, 3 g of divinyl benzene and 30 gof a low molecular weight, honey-line copolymer of isobutene andl-butene having an average molecular weight of 5,700 were dissolved into300 cc of heptane. The atmosphere was replaced by nitrogen and thetemperature was raised to 70 72 C., followed by addition of 1.2 g ofbenzoyl peroxide.

The polymerization was conducted for 3 hours. Several minutes afterinitiation of the polymerization the formation of a white slurry tookplace, and at completion of the polymerization the system was convertedto a highly viscous slurry containing a finely divided high polymer. Theyield was 75 percent.

The solvent was removed from the slurry by distillation in a porcelainvat, and the remaining solid was kneaded with an isotactic polypropylenein an amount such that the content of the finely divided high polymerwould be about 3 percent. As a result of the observation of thedispersion state of the finely divided high polymer it was confirmedthat the high polymer was dispersed in a good condition, though it was alittle inferior to the dispersion condition in the product of Example 1.Example 9 7.5 G of maleic anhydride, 6 g of styrene, b 1.5 g of divinylbenzene and 8 g of polybutene having an average molecular weight of 570were charged into a reactor together with 140 ml of benzene. Theatmosphere inside the reactor was replaced by nitrogen and thetemperature was raised to 79 C. to form a homogeneous solution. Then,0.6 g of benzoyl peroxide and 10 ml of benzene were charged into thereactor, and the polymerization was conducted for hours.

After completion of the polymerization, the solvent was removed from theresulting slurry. As a result there was obtained a waxy mixture of thepolybutene and a finely divided high polymer. The yield was 82 percent.The mixture was blend into an isotactic polypropylene in an amount suchthat the content of the finely divided high polymer would be about 3percent. Then, the dispersibility was examined in the same manner as inExample 1 and it was confirmed that the finely divided high polymer waspresent with an excellent dispersibility Example 26 G of glycidylmethacrylate, 4 g of divinyl benzene, 30 g of an atacticethylene-propylene copolymer having a molecular weight of about 7,000and containing 3.7 percent by weight of ethylene units, 1.6 g of benzoylperoxide and 270 cc of n-heptane were charged into a pressure-resistantglass reactor equipped with a stirrer. After the atmosphere inside thereactor had been replaced by nitrogen, the temperature was raised andthe polymerization was conducted at 86 87 C. for about 7 hours. Duringthe polymerization the pressure inside the reactor was 4.7 Kglcm As aresult there was obtained a white opaque slurry at a yield of 80 Theslurry was placed in a porcelain vat and dried in the air. Thus, therewas obtained a white power consisting of a finely divided high polymersprinkled on the waxy atactic copolymer. The powder was blended topowder of an isotactic polypropylene in an amount such that the contentof the finely divided high polymer would be about 3 Then, the blend wasextruded and shaped into a film having a thickness of 0.35 mm. The filmwas dyed in the same manner as in Example 1 and the section thereof wasobserved under a microscope. As a result, it was confirmed that thefinely divided high polymer was present in the uniformly dispersed statein the form of particles of a diameter of less than 0.5a.

Example 1 l 27 G of glycidyl acrylate, 3 g of divinyl benzene, 9 g ofpolyoxyethylene alkyl ether (Emargen, product of Kao Atlas Co.) and g ofa low molecular weight polyethylene having an average molecular weightof 5,400 were added into 235 cc of n-heptane, and the system was mixedwhile stirring at 80 C. under a nitrogen atmosphere to dissolve the lowmolecular weight polyethylene. Then, 1 g of benzoyl peroxide was flowninto the system together with cc of n-heptane. The polymerization wasconducted for 5 hours. A white slurry containing a finely divided highpolymer was obtained at a yield of 64 The slurry was placed in aporcelain vat and the solvent was removed therefrom at room temperature.The remaining solid was blended into polypropylene in an amount suchthat the content of the high polymer would be about 3 percent. The blendwas molded into a pellet by means of an extruder and then the dispersionstate was observed under a microscope in the same manner as inExample 1. It was confirmed that the finely divided high polymer wasquite uniformly dispersed.

Example 12 7.5 G of maleic anhydride, 6 g of styrene, 1.5 0g of divinylbenzene, 4 g of polyoxyethylene alkyl ether (Emargen, product of KaoAtlas Co.), 7.5 g of a low molecular weight polyethylene having amolecular weight of about 2,000 and ml of benzene were charged into areactor. The mixing was conducted under a nitrogen atmosphere at 79 C.until the low molecular weight polyethylene and maleic anhydride hadbeen dissolved. Thereafter, 0.5 g of azobisisobutyronitrile dissolved in10 ml of benzene was added into the reactor and the polymerization wasconducted for 2 hours to obtain a slurry at a yield of 66 percent. Theslurry was treated in the same manner as in Example 1 l to examine thedispersion state. As a result it was observed that a finely divided highpolymer was dispersed quite uniformly in the product.

Example 13 15 G of l-methyl-2-vinyl imidazole, 12 g of methylmethacrylate and 3 g of divinyl benzene were added to a solution of 30 gof a low molecular weight polyethylene having a molecular weight ofabout 2,000 in 220 cc of n-heptane maintained at 80 C. Then, 1 g ofbenzoyl peroxide was added together with 20 cc of n-heptane to thesystem under a nitrogen atmosphere while stirring, and thepolymerization was conducted for 5 hours. A slurry was obtained at ayield of 27 percent. The dispersibility was examined in accordance withthe procedures adopted in Example 1. As a result, it was confirmed thatfinely divided high polymer was quite uniformly dispersed in theproduct.

Example l4 15 G of maleic anhydride, 12 g of styrene and 3 g of divinylbenzene were dissolved into a solution of 15 g of a low molecular weightisotactic polypropylene having a molecular weight of about 8,000(obtained by thermally decomposing a high molecular weight isotacticpolypropylene having a melt index of 12 at 350 C. in vacuo) in 235 cc ofbenzene maintained at 80 C., followed by addition of l g of benzoylperoxide dissolved in 20 cc of benzene. The polymerization was conductedfor two hours to obtain a slurry at a yield of 89 percent. Thedispersibility was examined in the same manner as in Example 1 and itwas confirmed that a finely divided high polymer was dispersed quiteuniformly in the product. Example 15 The polymerization was conducted inthe same manner as in Example 1 except using 25 g of vinyl acetate and 5g of divinyl benzene to obtain a product at a monomer conversion of 21The dispersibility was examined in the same manner as in Example 1 andit was confirmed that a finely divided high polymer was quite uniformlydispersed in the product. Example 16 Run No. l was repeated by effectingthe initiation of the polymerization by means of a ultraviolet lampirradiation without using benzoyl peroxide, and the polymerization wasconducted at 25 C. for 30 hours. The yield was 53 percent. The resultingfinely divided high polymer exhibited an excellent dispersibilityequivalent to that of the high polymer of Example 1.

Example 17 270 G of glycidyl methacrylate, 30 g of divinyl benzene and gof an atactic ethylene-propylene copolymer having a molecular weight ofabout 7,000 and containing 3.7 percent by weight of ethylene units weredissolved in 2,500 cc of nheptane at 80 C. The polymerization wasconducted for 5 hours at 80 C. Under a nitrogen atmosphere whilestirring with the use of 9 g of benzoyl peroxide as an initiator. Theyield was 82 percent. The reaction product was placed in a porcelain vatand the solvent was removed by distillation. The resulting atacticcopolymer composition containing a finely divided high polymer waskneaded in Bumburrys mixer for minutes with a polypropylene pellet(having a melt index of 6.5 g/min at 230 C.) containing 2 percent of2,5-di-tert.- butyl-hydroxyl toluene and 4 percent of dilaurylthiodipropionate as antioxidants, and then, the mixture was subjected toan action of a crusher to obtain a chip-like polypropylene compositioncontaining 3 percent of a finely divided high polymer. Then, thecomposition was spun at 260 C. and drawn at a draw ratio of 4 at 125 C.to obtain a filament (A) of 3 deniers. Separately, the polymerizationwas conducted in the same manner as above in the absence of the atacticcopolymer, and the resulting polymeric composition was blended spun anddrawn in the same manner as above to obtain a filament (B). When bothfilaments were dyed under the same dyeing conditions, the filament (A)had considerably excellent color and luster as compared with thefilament (B). Further, the filament (A) exhibited an improved dyeexhaustion.

Dyeing were conducted at a dyestuff concentration of 3 percent o.w.f. ina water bath containing a soap (Monogen, product of Daiichi KogyoSeiyaku K. K.) a concentration of 1 g/l at a bath ratio of 40, at atemperature of 120 C. for 2 hours. The results are shown in Table 2below.

5 G of an atactic polypropylene having a molecular weight of about41,000 and 100 ml of kerosene were charged into a reactor. Theatmosphere inside the reactor was replaced by nitrogen, and thetemperature was raised to 1 18 C. while stirring until the atacticpolypropylene was completely dissolved in kerosene to form a transparentsolution. G of a mixture of glycidyl metharcylate and divinyl benzene(divinyl benzene content being 10 percent by weight) containing,dissolved therein, 0.3 g of benzoyl peroxide was added to the reactor bymeans of an injector, and the polymerization was conducted for 1.5hours. Just after the addition of the monomer mixed liquor, the systemtook the form ofa milky, uniform dispersion and this state wasmaintained throughout the polymerization. In order to terminate thepolymerization, 0.3 g of a polymerization inhibitor (2,5-di-tert.-butylcresol) was added to the polymerization system, followed by cooling. Asthe system was cooled, the atactic polypropylene was precipitated andthe system became jellied. The jellied product contained a finelydivided high polymer dispersed in the atactic polypropylene. The jelliedproduct was well mixed with an isotactic polypropylene in heptane in amanner such that the content of the finely divided high polymer of thejellied product would be about 3 percent, followed by filtration. To theresidue was added about 10 ml of an ether solution containing about 0.2percent, based on the isotactic polypropylene of 2,5-di-tert.-butylcresol. Then, they were well mixed, and the solvent was removedtherefrom. Thereafter, the remaining mixture was molded into a pellet bymeans of an extruder. Then, the dispersibility of the finely dividedhigh polymer was examined in the same manner as in Example 1 and it wasconfirmed that the high polymer was dispersed uniformly in a finelydivided state in the product. Example 19 The polymerization wasconducted in the same manner as in Example 19 except using an atacticethylene-propylene copolymer having a molecular weight of about 60,000instead of the atactic polypropylene and ligroin (fraction at C.) as thesolvent. it was confirmed that a finely divided high polymer wasuniformly dispersed in the product in a fine state as was observed inExample 18. Example 2O 10 G of a 5 4 l (by weight) mixture of acrylicacid amide, styrene and divinyl benzene 5 g of polypropylene oxidehaving an intrinsic viscosity of 3.2 were dissolved in 100 ml of a 70 230 (by weight) mixed solvent of heptane and isopropanol, followed byaddition of 0.3 g of benzoyl peroxide. The polymerization was conductedat 75 C. for 5 hours. The yield was 76 percent. The polymerizationproduct was subjected to the dispersibility examination test in the samemanner as in Example 1, and it was confirmed that a finely divided highpolymer was dispersed quite uniformly.

Example 1 10 G of a 4.5 4.5 1 (by weight) mixture of acrylic acid,methyl methacrylate and divinyl benzene and 5 g of an ethylene-vinylacetate copolymer Ultraccne, product of Japan Polychemical Co.; ethylenecontent 72 percent by weight) were dissolved into 100 ml of kerosene,followed by addition of 0.3 g of benzoyl peroxide, The polymerizationwas conducted at 80 C. for 2.5 hours. The yield was 88 percent. Thedispersibility examination test was conducted in the same manner as inExample 1, and it was confirmed that a finely divided high polymer wasuniformly dispersed in a good state.

What we claim is:

1. In a process for the preparation of finely divided high polymers of across-linked structure comprising polymerizing l. at least oneradical-polymerizable monoethylenically unsaturated monomer having anepoxy functional group; and

2. 0.5 to 30 percent by weight, based on the weight of saidmonoethylenically unsaturated monomer l of a diethylenically unsaturatedmonomer, in an organic solvent which dissolves said monomers 1) and (2)but not the cross-linked polymer produced therefrom and not thecorresponding linear polymer free of said diethylenically unsaturatedmonomer 2) in the presence of a free-radical initiator; the improvementwherein prior to the polymerization a linear hot n-heptane solublemonoolefin polymer is dissolved in said organic solvent in an amount of10 to 500 percent by weight based on the total weight of monomers l) and(2 2. The process of claim 1 wherein said organic solvent is present inan amount of more than 300 percent by weight based on the total weightof the monomers.

3. The process of claim 1 wherein said organic solvent is selected fromthe group consisting of aliphatic hydrocarbons, aliphatic alcohols of upto 8 carbon atoms, and linear or cyclic aliphatic ethers.

4. The process of claim 1 wherein said monoethylenically unsaturatedmonomer (a) is a glycidyl ester of an ethylenically unsaturatedcarboxylic acid.

5. The process of claim 1 wherein said monoolefin polymer is expressedby the formula:

wherein R represents hydrogen, an alkyl group of up to 4 carbon atoms orphenyl; and R represents hydrogen or an alkyl group of up to 4 carbonatoms.

6. The process of claim 1 wherein said monoethylenically unsaturatedmonomer is glycidyl methacrylate; said monoolefin polymer is an atacticethylene-propylene copolymer; and said diethylenically unsaturatedmonomer is divinyl benzene.

2. 0.5 to 30 percent by weight, based on the weight of saidmonoethylenically unsaturated monomer (1), of a diethylenicallyunsaturated monomer, in an organic solvent which dissolves said monomers(1) and (2) but not the cross-linked polymer produced therefrom and notthe corresponding linear polymer free of said diethylenicallyunsaturated monomer (2) in the presence of a free-radical initiator; theimprovement wherein prior to the polymerization a linear hot n-heptanesoluble monoolefin polymer is dissolved in said organic solvent in anamount of 10 to 500 percent by weight based on the total weight ofmonomers (1) and (2).
 2. The process of claim 1 wherein said organicsolvent is present in an amount of more than 300 percent by weight basedon the total weight of the monomers.
 3. The process of claim 1 whereinsaid organic solvent is selected from the group consisting of aliphatichydrocarbons, aliphatic alcohols of up to 8 carbon atoms, and linear orcyclic aliphatic ethers.
 4. The process of claim 1 wherein saidmonoethylenically unsaturated monomer (a) is a glycidyl ester of anethylenically unsaturated carboxylic acid.
 5. The process of claim 1wherein said monoolefin polymer is expressed by the formula: wherein R1represents hydrogen, an alkyl group of up to 4 carbon atoms or phenyl;and R2 represents hydrogen or an alkyl group of up to 4 carbon atoms. 6.The process of claim 1 wherein said monoethylenically unsaturatedmonomer is glycidyl methacrylate; said monoolefin polymer is an atacticethylene-propylene copolymer; and said diethylenically unsaturatedmonomer is divinyl benzene.